CA1147970A - Process for cobalt recovery from mixed sulfides - Google Patents
Process for cobalt recovery from mixed sulfidesInfo
- Publication number
- CA1147970A CA1147970A CA000367465A CA367465A CA1147970A CA 1147970 A CA1147970 A CA 1147970A CA 000367465 A CA000367465 A CA 000367465A CA 367465 A CA367465 A CA 367465A CA 1147970 A CA1147970 A CA 1147970A
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- CA
- Canada
- Prior art keywords
- cobalt
- nickel
- accordance
- slurry
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0492—Separation of nickel from cobalt in ammoniacal type solutions
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Abstract of the Disclosure The metal content of nickel-cobalt mixed sulfide slurries is recovered by atmospheric oxidation leaching, thereafter removing dissolved copper by metathesis with further mixed sulfide feed, treating the filtrate after liquid-solids separation with ammonia to selectively precipitate cobalt, separating the cobalt precipitate and working up the resulting filtrate to recover nickel.
Description
~7970 PRIOR ART AND BACRGROUND OF T~E INVENTION
In the hydrometallurgical treatment of ores contain-ing nickel cobalt and/or copper, by-product sulfides containing the metals cobalt, nickel and/or copper may be generated in various points in the process. As an example, the purification of nickel bearing ammoniacal leach liquors to remove cobalt and copper can produce precipitates which are usually in the form of a thickener underflow or a filter cake and which contain up to 75% moisture. These materials are finely divided and may include, besides the valuable metals cobalt, nickel and copper various other impurities and residual ammonia. These materials are difficult to treat and at pre-sent the only known ways of treating them for the purpose of recovering metal values involve leaching at elevated tem-perature and pressure. Such a process is described in a paper presented at 109 AIME Annual Meeting, Las Vegas, Nevada, U.S.A. in February, 1980 by Suetsuma et al. Treatment of materials at elevated temperature and pressure in autoclaves is expensive and it would be desirable to provide a means for treating nickel, cobalt, copper sulfide residues at atmospheric pressure. In this connection the atmospheric leaching of mattes is known and is described for example in a paper entitled, "Atmospheric Leaching of Matte at the Port Nickel Refinery" by Llanos et al, which appeared in the CIM
Bulletin, February, 1974, pages 74-81. The known atmospheric leaching processes seem to involve the treatment of matte with an acid solution having a high copper content such as spent copper electrowinning electrolyte depleted with respect to copper and having a considerable content of acid. When ~F -~L47970 solutions are reacted with matte, a eementation reaction occurs with precipitation of the copper eontent of the solution and solubilization of nickel and cobalt values in the matte.
The economic utilization of such a proeess depends, of course, on the ready availability of acid solutions containing copper.
It is also known from the work of Dr. -Ing Hans Grothe dating back to the 1930's (German Patent No. 595,688) that ammonia may be used in the treatment of a water solution of cobalt and nickel sulfates to precipitate cobalt and provide a cobalt precipitate depleted in nickel and a solution enriched in nickel and depleted in cobalt. U.S. Patent No. 3,751,558 is also relevant.
Materials to the treatment of which the invention is particularly directed will usually contain, on a dry basis, about 0.5% to about 15% eobalt, about 5% to about 30% niekel up to about 25% eopper, up to about 15% iron and about 15% to about 30% sulfur. The materials usually oeeur as a result of sulfide preeipitation from solution to reeover the metal eontent thereof.
The materials may also eontain up to about 8% ammonia from prior proeessing.
Statement of the Invention The present invention may be generally defined as a proeess for separating niekel and eobalt eontained in a mixed niekel-eobalt sulfide material which eomprises slurrying said sulfide material in an aqueous medium, oxidatively leaehing said slurry at a pH in the range of neutral to slightly aeid with an oxygen eontaining gas and agitation for a time suffieient to dissolve a substantial quantity of the eobalt and niekel eontents thereof, and thereafter preeipitating eobalt from the resulting solution with ammonia to provide a niekel-depleted eobalt preeipitate and a eobalt-depleted niekel solution.
B
~47970 Desirably the ammonia content, if any, of the feed material should be controlled to a value not exceeding about 10 grams per liter ammonia. Otherwise crystallization of a mixed ammonium sulfate, metal sulfate salt may occur undesirably.
The ammonia content of the initial material can be removed and recovered by known methods.
~r~ he -~h~ leach slurry is subjected to oxidative leaching at atmospheric pressure using air as an oxidant and with good agitation. The leaching process occurs at a pH which is essentially neutral to only slightly acidic. Thus, depending upon the presence of ammonia in the starting mate-rial, the initial pH of the feed slurry may be in a range of about pH 5 to about pH 8. The reaction temperature and rate of air addition may be varied rather widely. For example, the temperature employed may lie in a range of about 40C to about 100C while the rate of air addition should be between 0.05 liters per liter of slurry per minute and several, e.g., 5, liters per liter of slurry per minute. Economically, a reaction temperature of about 70C to about 80C and a rate of air addition of about 0.3 to about 0.5 liters per liter of slurry per minute is satisfactory. It is found that the heat generated by the oxidation of sulfides to sulfate is approximately that equal to the heat removed from the system by the exiting air stream saturated with water vapor at the reaction temperature. Agitation is employed so as to effect good contact between the solids being leached and the active oxidative reagent namely oxygen. In general, leaching is completed in about 8 hours to about 40 hours.
~7~70 Many mixed sulfide materials to be treated may contain copper sulfide which is undesirable in a final cobalt or nickel product. The amount of copper dissolved can be limited by monitoring the pH of the leach slurry. To the extent that dissolution of copper occurs during oxidative leaching, it is found that the concentration of copper can be reduced and the additional benefit of dissolving still further quantities of nickel and cobalt can be affected by a metathetic leaching between the leached copper and nickel and cobalt sulfides. The metathetic leach preferably is carried out in a temperature range of about 70 to 80C and is conducted in the absence of aeration. Desirably, the pH
of leach slurry is adjusted to approximately pH 5 during the metathetic leach so as to increase the extraction of cobalt and nickel from the fresh sulfide material and to reduce the concentration of copper. Upon the completion of the leach, the slurry is subjected to solid-liquid separation to recover the leach liquor containing dissolved cobalt and nickel values.
The residue can either be rejected or treated further depending on the metal value content thereof.
The leach liquor is then treated for cobalt recovery and desirably to effect as much as possible the separation of cobalt and nickel. A preferred method to accomplish this result is to treat the leach liquor with ammonia at a pH of approximately 8.3 to effect selective precipitation of cobalt.
Either anhydrous or aqueous ammonia can be used. The reaction can be carried out for example in an agitated tank at an operating temperature of about 60C, although a temperature in the range of about 40C to about 80C may be employed.
~7~70 The resulting cobalt precipitate is separated by thickening and/or filtration and the filtrate is then treated for nickel recovery.
EXAMPL~ I (batch leaching) A mixed sulfide filter cake analyzing by weight 1.62% cobalt, 17% nickel, 26.5% copper, 1.15% selenium, 4.1%
iron, 19% sulfur was pulped in water to provide two liters of slurry containing 20% solids by weight. The feed slurry was charged to a 2.5 liter baffled vessel equipped with a 2-inch diameter radial turbine turning at 1000 rpm. The vessel was supplied with air at atmospheric pressure at a rate of 0.32 liters per liter of slurry per minute. The solution was assayed for metal values and pH at various times over a leaching period of 21.5 hours with the results shown in the following Table I.
Table I
Leaching Solution Assay, 9/1 pH at Time h CoNi Cu Se Fe 22C
In the hydrometallurgical treatment of ores contain-ing nickel cobalt and/or copper, by-product sulfides containing the metals cobalt, nickel and/or copper may be generated in various points in the process. As an example, the purification of nickel bearing ammoniacal leach liquors to remove cobalt and copper can produce precipitates which are usually in the form of a thickener underflow or a filter cake and which contain up to 75% moisture. These materials are finely divided and may include, besides the valuable metals cobalt, nickel and copper various other impurities and residual ammonia. These materials are difficult to treat and at pre-sent the only known ways of treating them for the purpose of recovering metal values involve leaching at elevated tem-perature and pressure. Such a process is described in a paper presented at 109 AIME Annual Meeting, Las Vegas, Nevada, U.S.A. in February, 1980 by Suetsuma et al. Treatment of materials at elevated temperature and pressure in autoclaves is expensive and it would be desirable to provide a means for treating nickel, cobalt, copper sulfide residues at atmospheric pressure. In this connection the atmospheric leaching of mattes is known and is described for example in a paper entitled, "Atmospheric Leaching of Matte at the Port Nickel Refinery" by Llanos et al, which appeared in the CIM
Bulletin, February, 1974, pages 74-81. The known atmospheric leaching processes seem to involve the treatment of matte with an acid solution having a high copper content such as spent copper electrowinning electrolyte depleted with respect to copper and having a considerable content of acid. When ~F -~L47970 solutions are reacted with matte, a eementation reaction occurs with precipitation of the copper eontent of the solution and solubilization of nickel and cobalt values in the matte.
The economic utilization of such a proeess depends, of course, on the ready availability of acid solutions containing copper.
It is also known from the work of Dr. -Ing Hans Grothe dating back to the 1930's (German Patent No. 595,688) that ammonia may be used in the treatment of a water solution of cobalt and nickel sulfates to precipitate cobalt and provide a cobalt precipitate depleted in nickel and a solution enriched in nickel and depleted in cobalt. U.S. Patent No. 3,751,558 is also relevant.
Materials to the treatment of which the invention is particularly directed will usually contain, on a dry basis, about 0.5% to about 15% eobalt, about 5% to about 30% niekel up to about 25% eopper, up to about 15% iron and about 15% to about 30% sulfur. The materials usually oeeur as a result of sulfide preeipitation from solution to reeover the metal eontent thereof.
The materials may also eontain up to about 8% ammonia from prior proeessing.
Statement of the Invention The present invention may be generally defined as a proeess for separating niekel and eobalt eontained in a mixed niekel-eobalt sulfide material which eomprises slurrying said sulfide material in an aqueous medium, oxidatively leaehing said slurry at a pH in the range of neutral to slightly aeid with an oxygen eontaining gas and agitation for a time suffieient to dissolve a substantial quantity of the eobalt and niekel eontents thereof, and thereafter preeipitating eobalt from the resulting solution with ammonia to provide a niekel-depleted eobalt preeipitate and a eobalt-depleted niekel solution.
B
~47970 Desirably the ammonia content, if any, of the feed material should be controlled to a value not exceeding about 10 grams per liter ammonia. Otherwise crystallization of a mixed ammonium sulfate, metal sulfate salt may occur undesirably.
The ammonia content of the initial material can be removed and recovered by known methods.
~r~ he -~h~ leach slurry is subjected to oxidative leaching at atmospheric pressure using air as an oxidant and with good agitation. The leaching process occurs at a pH which is essentially neutral to only slightly acidic. Thus, depending upon the presence of ammonia in the starting mate-rial, the initial pH of the feed slurry may be in a range of about pH 5 to about pH 8. The reaction temperature and rate of air addition may be varied rather widely. For example, the temperature employed may lie in a range of about 40C to about 100C while the rate of air addition should be between 0.05 liters per liter of slurry per minute and several, e.g., 5, liters per liter of slurry per minute. Economically, a reaction temperature of about 70C to about 80C and a rate of air addition of about 0.3 to about 0.5 liters per liter of slurry per minute is satisfactory. It is found that the heat generated by the oxidation of sulfides to sulfate is approximately that equal to the heat removed from the system by the exiting air stream saturated with water vapor at the reaction temperature. Agitation is employed so as to effect good contact between the solids being leached and the active oxidative reagent namely oxygen. In general, leaching is completed in about 8 hours to about 40 hours.
~7~70 Many mixed sulfide materials to be treated may contain copper sulfide which is undesirable in a final cobalt or nickel product. The amount of copper dissolved can be limited by monitoring the pH of the leach slurry. To the extent that dissolution of copper occurs during oxidative leaching, it is found that the concentration of copper can be reduced and the additional benefit of dissolving still further quantities of nickel and cobalt can be affected by a metathetic leaching between the leached copper and nickel and cobalt sulfides. The metathetic leach preferably is carried out in a temperature range of about 70 to 80C and is conducted in the absence of aeration. Desirably, the pH
of leach slurry is adjusted to approximately pH 5 during the metathetic leach so as to increase the extraction of cobalt and nickel from the fresh sulfide material and to reduce the concentration of copper. Upon the completion of the leach, the slurry is subjected to solid-liquid separation to recover the leach liquor containing dissolved cobalt and nickel values.
The residue can either be rejected or treated further depending on the metal value content thereof.
The leach liquor is then treated for cobalt recovery and desirably to effect as much as possible the separation of cobalt and nickel. A preferred method to accomplish this result is to treat the leach liquor with ammonia at a pH of approximately 8.3 to effect selective precipitation of cobalt.
Either anhydrous or aqueous ammonia can be used. The reaction can be carried out for example in an agitated tank at an operating temperature of about 60C, although a temperature in the range of about 40C to about 80C may be employed.
~7~70 The resulting cobalt precipitate is separated by thickening and/or filtration and the filtrate is then treated for nickel recovery.
EXAMPL~ I (batch leaching) A mixed sulfide filter cake analyzing by weight 1.62% cobalt, 17% nickel, 26.5% copper, 1.15% selenium, 4.1%
iron, 19% sulfur was pulped in water to provide two liters of slurry containing 20% solids by weight. The feed slurry was charged to a 2.5 liter baffled vessel equipped with a 2-inch diameter radial turbine turning at 1000 rpm. The vessel was supplied with air at atmospheric pressure at a rate of 0.32 liters per liter of slurry per minute. The solution was assayed for metal values and pH at various times over a leaching period of 21.5 hours with the results shown in the following Table I.
Table I
Leaching Solution Assay, 9/1 pH at Time h CoNi Cu Se Fe 22C
2 0.0310.92 0.005 0.004 --- 8.1 4 0.3403.52 0.001 O.OQ5 --- 7.2 5.5 0.756.46 0.005 0.008 --- 6.95 7.5 1.3711.0 0.002 0.017 --- 6.65 9.5 1.9715.9 0.012 0.028 --- 6.42 11.0 2.2118.2 0.060 0.026 --- 6.25 15.5 2.9023.2 0.320 0.045 --- 5.62 18.0 3.2526.6 0.810 0.033 --- 5.45 21.5 3.4529.6 1.29 0.026 <0.001 5.25 The results given in Table I demonstrate an extraction of 89.6% cobalt, 73.3% nickel, 2% copper and 0.9% selenium.
50 grams of the initial feed cake were then added to the leach slurry and the leaching carried out without aeration for four hours with the recults in the following Table II.
-1~79~0 Table II
Time, h Co Ni Cu Se Fe pH
2 3.75 30.1 0.290 0.003 <0.001 5.65 4 3.75 30.1 0.019 0.002 0.001 5.50 The overall extraction including that derived from metathetic leaching represented 93.7% cobalt, 71.7% nickel, 0.03% copper and 0.07% selenium.
EXAMPLE II
A series of four batch runs was made at atmospheric pressure usin~ a mixed sulfide precipitate pulped in water.
In each case the feed employed originated from the ammoniacal leaching of a lateritic ore and contained on a dry basis 34.6~ nickel, 8.76% cobalt, 0.93% copper, 1% iron and 27.4%
total sulfur. The precipitate was dried and then repulped lS in water to 10% solids. The same reactor was employed as in Example I with an air rate of 0.5 liters per liter of slurry per minute. The results obtained in the four tests are set forth in the following Tables III through VI and the rates of extraction for the five tests of Examples I and II are given in Table VII.
79'~0 Table III
Test Time Solution, 9/1 Ni~Co TemP.
No. h Ni Co Cu Fe pH mol/l C
0 2.80 0.34 <.001 <.001 7.2 .053 22 0 3.50 0.28 <.001 <.001 7.2 .064 80 5.00 0.38 < .001 <.001 6.6 .091 2 7.20 0.66 <.001 <.001 6.5 0.13 2 4 12.0 1.40 <.0~1 <.001 6.2 0.23 14.8 2.00 <.001 <.001 6.1 0.28 6 17.0 2.40 <.001 <.001 6.0 0.33 7 18.8 3.00 <.001 <.001 5.8 0.37 11.6 19.7 6.12 <.001 0.23 4.0 0.610 23 37.4 9.12 0.92 0.62 2.8 0.792 24 37.4 9.27 1.16 0.64 2.7 0.794 Table IV
TestTime Solution, g/l Ni~Co TemP.
No. h Ni Co Cu Fe pH mol/l C
0 4.20 0.41 <.001 <.001 7.3 .078 70 2 7.92 0.83 <.001 <.001 7.15 0.15 4 12.8 1.70 <.001 <.001 6.9 0.24
50 grams of the initial feed cake were then added to the leach slurry and the leaching carried out without aeration for four hours with the recults in the following Table II.
-1~79~0 Table II
Time, h Co Ni Cu Se Fe pH
2 3.75 30.1 0.290 0.003 <0.001 5.65 4 3.75 30.1 0.019 0.002 0.001 5.50 The overall extraction including that derived from metathetic leaching represented 93.7% cobalt, 71.7% nickel, 0.03% copper and 0.07% selenium.
EXAMPLE II
A series of four batch runs was made at atmospheric pressure usin~ a mixed sulfide precipitate pulped in water.
In each case the feed employed originated from the ammoniacal leaching of a lateritic ore and contained on a dry basis 34.6~ nickel, 8.76% cobalt, 0.93% copper, 1% iron and 27.4%
total sulfur. The precipitate was dried and then repulped lS in water to 10% solids. The same reactor was employed as in Example I with an air rate of 0.5 liters per liter of slurry per minute. The results obtained in the four tests are set forth in the following Tables III through VI and the rates of extraction for the five tests of Examples I and II are given in Table VII.
79'~0 Table III
Test Time Solution, 9/1 Ni~Co TemP.
No. h Ni Co Cu Fe pH mol/l C
0 2.80 0.34 <.001 <.001 7.2 .053 22 0 3.50 0.28 <.001 <.001 7.2 .064 80 5.00 0.38 < .001 <.001 6.6 .091 2 7.20 0.66 <.001 <.001 6.5 0.13 2 4 12.0 1.40 <.0~1 <.001 6.2 0.23 14.8 2.00 <.001 <.001 6.1 0.28 6 17.0 2.40 <.001 <.001 6.0 0.33 7 18.8 3.00 <.001 <.001 5.8 0.37 11.6 19.7 6.12 <.001 0.23 4.0 0.610 23 37.4 9.12 0.92 0.62 2.8 0.792 24 37.4 9.27 1.16 0.64 2.7 0.794 Table IV
TestTime Solution, g/l Ni~Co TemP.
No. h Ni Co Cu Fe pH mol/l C
0 4.20 0.41 <.001 <.001 7.3 .078 70 2 7.92 0.83 <.001 <.001 7.15 0.15 4 12.8 1.70 <.001 <.001 6.9 0.24
3 6 17.6 2.95 <.001 <.001 6.6 0.35 9 26.0 5.61 <.001 .002 5.3 0.53 24 37.5 9.26 1.06 0.65 1.9 0.79 Table V
TestTime Solution, 9/1 Ni~Co TemP.
No. h Ni Co Cu _ Fe pH mol/l C
0 4.19 0.43 <.001 <.001 6.9 .978 ~0 2 7.08 0.68 <.001 <.001 6.8 0.13
TestTime Solution, 9/1 Ni~Co TemP.
No. h Ni Co Cu _ Fe pH mol/l C
0 4.19 0.43 <.001 <.001 6.9 .978 ~0 2 7.08 0.68 <.001 <.001 6.8 0.13
4 10.2 1.20 <.001 <.001 6.7 0.19 4 6 15.0 2.18 <.001 <.001 6.65 0.29 9 24.6 4.12 <.001 ~001 5.4 0.49 24 37.5 8.97 1.10 0.69 2.6 0.79 ~7970 Table VI
Test Time Solution, g/l Ni~Co Temp.
No. h Ni Co Cu Fe pHmol/1 C
0 3.180.29<.001 <.001 7.2.059 50 2 5.640.47<.001 <.001 7.00.10 4 7.970.76<.001 <.001 6.950.15 6 9.821.02<.001 <.001 6.90.18 7.5 11.91.43<.001 <.001 6.80.22 24 27.26.30.~18 <.001 5.80.57 27 30.37.24.053 <.001 5.60.64 36.39.00.156 <.001 5.50.77 Table VII
Test Temperature Air RateRate of Leaching No.(C) ___ 11~ (slurry/min) (mol Me++/Q.h)*
1 80 0.32 0.0286 2 80 0.50 0.044 3 70 0.50 0.044 4 60 0.50 0.0270 0.50 0.0215 *mol Me== = Co + Ni + Cu E~CAMPLE III
Two 28 liter baffled vessels equipped with a six-inch diameter radial turbine rotating at 333 rpm were set up in series such that slurry from the first reactor for oxida-tive leaching was fed to the second reactor for metathetic leaching with a residence time of slurry in each reactor of 24 hours. A temperature of 70C was employed in each reactor with reactions in each being conducted at atmospheric pressure.
The air rate in the first reactor was maintained in the range of 0.2 to 0.26 liters per liter of slurry per minute. The second reactor for metathetic leaching was not aerated. The pH in the metathetic leach reactor was maintained at about ~47970 4.9 by sulfuric acid addition. The system was operated over a period of time of 300 hours during which period 432 kilo-grams of material were treated. The sulfide precipitate treated analyzed, in weight percent 1.03% cobalt, 11.1% nickel, 16.8% copper, 7.1% iron, 0.008% zinc, 1.53% magnesium and 14.3% sulfur which was pulped in water to 15% solids. The overall results are shown in the following Table VIII.
Table VIII
1st Reactor (Oxidative Leaching) Co Ni Cu Leaching liquor (g/l)1.04 5.9 0.046 Extraction (%) 55.0 32.0 0 2nd Reactor tpH Adj/Metathetic Leaching) Co Ni Cu Leach liquor (g/l) 1.5 10.9 0.8 Extraction (%) 85.0 59.0 3.0 Although the feed material was of a relatively low grade, a satisfactory extraction of Co of 85% was achieved.
ÆXAMPLÆ IV
(continuous cobalt precipitation) A liquor analyzing in grams per liter 3~83 cobalt and 16.1 nickel at pH of 5 was fed continually to a 0.5 liter baffled vessel equipped with a 1.25-inch diameter radial turbine turning at 500 rpm, at a rate to provide an average residence time of liquor in the vessel of 5 minutes. The precipitant comprising a 200 gram per liter aqueous ammonia solution was added to the liquor on demand to maintain a pH
~7970 of 9 at a temperature of 60C. The precipitate was filtered and both the filtrate and precipitate analyzed for cobalt and nickel with the results shown in the following Table IX.
Table IX
Co Ni Filtrate (g/l) 0.152 10.8 Precipitate (%) 25.4 20.6 % Precipitated 95.1 18.2 EXAMPLE V
The run shown in Example IV was repeated using a liquor analyzing in grams per liter 3.92 cobalt and 16.8 nickel at pH 5. In the test of this Example, anhydrous ammonia was used instead of aqueous ammonia and the results 15are shown in the following Table X.
Table X
Co Ni Filtrate (g/l) 0.985 15.6 Precipitate (%) 39.6 13.9 % Precipitated 73.3 5.7 EXAMPLE VI
A leach liquor from a continuous leaching run analyzing 2.68 grams per liter cobalt, 11.8 grams per liter nickel, 0.44 grams per liter copper, 0.033 grams per liter selenium, 0.0011 grams per liter zinc, 0.081 grams per liter magnesium, 3.52 grams per liter ammonia and having a pH of
Test Time Solution, g/l Ni~Co Temp.
No. h Ni Co Cu Fe pHmol/1 C
0 3.180.29<.001 <.001 7.2.059 50 2 5.640.47<.001 <.001 7.00.10 4 7.970.76<.001 <.001 6.950.15 6 9.821.02<.001 <.001 6.90.18 7.5 11.91.43<.001 <.001 6.80.22 24 27.26.30.~18 <.001 5.80.57 27 30.37.24.053 <.001 5.60.64 36.39.00.156 <.001 5.50.77 Table VII
Test Temperature Air RateRate of Leaching No.(C) ___ 11~ (slurry/min) (mol Me++/Q.h)*
1 80 0.32 0.0286 2 80 0.50 0.044 3 70 0.50 0.044 4 60 0.50 0.0270 0.50 0.0215 *mol Me== = Co + Ni + Cu E~CAMPLE III
Two 28 liter baffled vessels equipped with a six-inch diameter radial turbine rotating at 333 rpm were set up in series such that slurry from the first reactor for oxida-tive leaching was fed to the second reactor for metathetic leaching with a residence time of slurry in each reactor of 24 hours. A temperature of 70C was employed in each reactor with reactions in each being conducted at atmospheric pressure.
The air rate in the first reactor was maintained in the range of 0.2 to 0.26 liters per liter of slurry per minute. The second reactor for metathetic leaching was not aerated. The pH in the metathetic leach reactor was maintained at about ~47970 4.9 by sulfuric acid addition. The system was operated over a period of time of 300 hours during which period 432 kilo-grams of material were treated. The sulfide precipitate treated analyzed, in weight percent 1.03% cobalt, 11.1% nickel, 16.8% copper, 7.1% iron, 0.008% zinc, 1.53% magnesium and 14.3% sulfur which was pulped in water to 15% solids. The overall results are shown in the following Table VIII.
Table VIII
1st Reactor (Oxidative Leaching) Co Ni Cu Leaching liquor (g/l)1.04 5.9 0.046 Extraction (%) 55.0 32.0 0 2nd Reactor tpH Adj/Metathetic Leaching) Co Ni Cu Leach liquor (g/l) 1.5 10.9 0.8 Extraction (%) 85.0 59.0 3.0 Although the feed material was of a relatively low grade, a satisfactory extraction of Co of 85% was achieved.
ÆXAMPLÆ IV
(continuous cobalt precipitation) A liquor analyzing in grams per liter 3~83 cobalt and 16.1 nickel at pH of 5 was fed continually to a 0.5 liter baffled vessel equipped with a 1.25-inch diameter radial turbine turning at 500 rpm, at a rate to provide an average residence time of liquor in the vessel of 5 minutes. The precipitant comprising a 200 gram per liter aqueous ammonia solution was added to the liquor on demand to maintain a pH
~7970 of 9 at a temperature of 60C. The precipitate was filtered and both the filtrate and precipitate analyzed for cobalt and nickel with the results shown in the following Table IX.
Table IX
Co Ni Filtrate (g/l) 0.152 10.8 Precipitate (%) 25.4 20.6 % Precipitated 95.1 18.2 EXAMPLE V
The run shown in Example IV was repeated using a liquor analyzing in grams per liter 3.92 cobalt and 16.8 nickel at pH 5. In the test of this Example, anhydrous ammonia was used instead of aqueous ammonia and the results 15are shown in the following Table X.
Table X
Co Ni Filtrate (g/l) 0.985 15.6 Precipitate (%) 39.6 13.9 % Precipitated 73.3 5.7 EXAMPLE VI
A leach liquor from a continuous leaching run analyzing 2.68 grams per liter cobalt, 11.8 grams per liter nickel, 0.44 grams per liter copper, 0.033 grams per liter selenium, 0.0011 grams per liter zinc, 0.081 grams per liter magnesium, 3.52 grams per liter ammonia and having a pH of
5.8 was fed to the reactor employed in Example IV. A resid-ence time in the reactor of 1 minute was employed and ~7970 anhydrous ammonia was used as a precipitant. The temperature was maintained at about 60C and the pH in the range of 8.2 to 8.3. One hundred eighty liters of the leach liquor were processed as described. The precipitate was settled and the underflow filtered and both the filtrate and the precipitate analyzed with the results shown in the following Table XI.
Table XI
Co Ni Cu Se NH3 Filtrate (g/l) 0.49 9.85 0.41 0.015 15.3 Precipitate t%) 29.2 18.0 0.44 0.21 _ % Precipitated 81.7 16.5 6.8 54.5 Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the inven-tion, as those skilled in the art will readily understand.
Such modifications and variations are considered to be within the purview and scope of the invention and appended claims.
Table XI
Co Ni Cu Se NH3 Filtrate (g/l) 0.49 9.85 0.41 0.015 15.3 Precipitate t%) 29.2 18.0 0.44 0.21 _ % Precipitated 81.7 16.5 6.8 54.5 Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the inven-tion, as those skilled in the art will readily understand.
Such modifications and variations are considered to be within the purview and scope of the invention and appended claims.
Claims (11)
1. A process for separating nickel and cobalt contained in a mixed nickel-cobalt sulfide material which comprises slurrying said sulfide material in an aqueous medium, oxida-tively leaching said slurry at a pH in the range of neutral to slightly acid with an oxygen containing gas and agitation for a time sufficient to dissolve a substantial quantity of the cobalt and nickel contents thereof, and thereafter pre-cipitating cobalt from the resulting solution with ammonia to provide a nickel-depleted cobalt precipitate and a cobalt-depleted nickel solution.
2. A process in accordance with claim 1 wherein the initial sulfide material also contains copper some of which is dissolved with the cobalt and nickel, and wherein at least a portion of the resulting solution is used wihtout aeration to leach an additional amount of said sulfide material to dissolve additional nickel and cobalt therefore in metathetic exchange with copper.
3. A process in accordance with claim 1 wherein the initial sulfide material contains, on a dry basis, about 0.5% to about 15% cobalt, about 5% to about 30% nickel, up to about 25% copper and about 15% to about 30% sulfur.
4. A process according to claim 1 wherein the initial feed material slurry contains no more than about 15 grams per liter of ammonia.
5. A process in accordance with claim 1 wherein the feed slurry has a solid content of about 5% to about 30% by weight.
6. A process in accordance with claim 5 wherein the solid content of the slurry is about 15% to about 20% by weight.
7. A process in accordance with claim 1 wherein the rate of air addition is at least 0.05 liters per liter of slurry per minute.
8. A process in accordance with claim 1 wherein the rate of air addition is about 0.,3 to about 0.5 liters per liter of slurry per minute.
9. A process in accordance with claim 1 wherein the reaction temperature is between about 40° and about 100°C.
10. A process in accordance with claim 1 wherein the reaction temperature is about 70°C.
11. A process in accordance with claim 2 wherein the metathetic leach is conducted at a temperature of about 70°C
to about 80°C and the slurry pH is about 5.
to about 80°C and the slurry pH is about 5.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000367465A CA1147970A (en) | 1980-12-23 | 1980-12-23 | Process for cobalt recovery from mixed sulfides |
| US06/298,208 US4401630A (en) | 1980-12-23 | 1981-08-31 | Process for cobalt recovery from mixed sulfides |
| GB8137510A GB2089776B (en) | 1980-12-23 | 1981-12-11 | Recovery and separation of nickel and cobalt |
| PH26650A PH19383A (en) | 1980-12-23 | 1981-12-18 | Process for cobalt recovery from mixed sulfides |
| FR8123808A FR2496700A1 (en) | 1980-12-23 | 1981-12-21 | PROCESS FOR SEPARATING AND RECOVERING NICKEL AND COBALT |
| JP56205359A JPS57131332A (en) | 1980-12-23 | 1981-12-21 | Recovery of cobalt from mixed sulfides |
| AU78718/81A AU548582B2 (en) | 1980-12-23 | 1981-12-21 | Recovering and separating nickel and cobalt from sulphides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000367465A CA1147970A (en) | 1980-12-23 | 1980-12-23 | Process for cobalt recovery from mixed sulfides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1147970A true CA1147970A (en) | 1983-06-14 |
Family
ID=4118771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367465A Expired CA1147970A (en) | 1980-12-23 | 1980-12-23 | Process for cobalt recovery from mixed sulfides |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4401630A (en) |
| JP (1) | JPS57131332A (en) |
| AU (1) | AU548582B2 (en) |
| CA (1) | CA1147970A (en) |
| FR (1) | FR2496700A1 (en) |
| GB (1) | GB2089776B (en) |
| PH (1) | PH19383A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6949232B2 (en) | 2002-05-31 | 2005-09-27 | Sherritt International Corporation | Producing cobalt (III) hexammine sulfate from nickel cobalt sulfides |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61130434A (en) * | 1984-11-30 | 1986-06-18 | Nippon Mining Co Ltd | Method for exuding sulfide containing nickel and/or cobalt |
| PT100091A (en) * | 1991-02-06 | 1993-05-31 | Denehurst Ltd | METHOD OF CONDITIONING A MATERIAL CARRYING OUT A BASIC METAL AND PRODUCING A CONCENTRATE OF A BASIC METAL |
| BRPI0604853B1 (en) * | 2006-10-27 | 2016-03-08 | Vale Do Rio Doce Co | Method for the production of metallic cobalt from nickel solvent extraction refining |
| JPWO2012017928A1 (en) * | 2010-08-03 | 2013-10-03 | 株式会社アクアテック | Method for oxidizing nickel sulfide in nickel sulfide-containing sludge, and method for recovering metallic nickel from nickel sulfide-containing sludge |
| PE20170515A1 (en) * | 2014-09-12 | 2017-05-18 | Smidth As F L | SYSTEM AND METHOD FOR ENHANCED METAL RECOVERY DURING ATMOSPHERIC LEACHING OF METAL SULFIDES |
| CA2968245C (en) * | 2014-11-20 | 2022-06-14 | Flsmidth A/S | System and method for enhanced metal recovery during atmospheric leaching of metal sulfides |
| AU2015364241B2 (en) * | 2014-12-19 | 2017-11-16 | Flsmidth A/S | Methods for rapidly leaching chalcopyrite |
| JP6897466B2 (en) | 2017-09-29 | 2021-06-30 | 住友金属鉱山株式会社 | How to separate copper from nickel and cobalt |
| JP6915497B2 (en) | 2017-10-23 | 2021-08-04 | 住友金属鉱山株式会社 | How to separate copper from nickel and cobalt |
| JP6939506B2 (en) | 2017-12-18 | 2021-09-22 | 住友金属鉱山株式会社 | How to separate copper from nickel and cobalt |
| CN109110827B (en) * | 2018-11-20 | 2020-06-26 | 安阳师范学院 | Preparation method and application of nickel disulfide nanospheres |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2588265A (en) * | 1949-11-15 | 1952-03-04 | Chemical Construction Corp | Isolation of nickel sulfide |
| US3616331A (en) * | 1968-08-03 | 1971-10-26 | Int Nickel Co | Recovery of nickel and copper from sulfides |
| US3652265A (en) * | 1969-11-28 | 1972-03-28 | Engelhard Min & Chem | Recovery of metal values from nickel-copper mattes |
| US3751558A (en) * | 1972-01-14 | 1973-08-07 | American Metal Climax Inc | Process of separating cobalt from nickel by means of ammonia |
| CA1106617A (en) * | 1978-10-30 | 1981-08-11 | Grigori S. Victorovich | Autoclave oxidation leaching of sulfide materials containing copper, nickel and/or cobalt |
| FI64188C (en) * | 1979-06-29 | 1983-10-10 | Outokumpu Oy | FOER FARING FOR SELECTIVE LAKING AV NICKEL-KOPPARSKAERSTEN |
| US4312841A (en) * | 1980-06-25 | 1982-01-26 | Uop Inc. | Enhanced hydrometallurgical recovery of cobalt and nickel from laterites |
-
1980
- 1980-12-23 CA CA000367465A patent/CA1147970A/en not_active Expired
-
1981
- 1981-08-31 US US06/298,208 patent/US4401630A/en not_active Expired - Lifetime
- 1981-12-11 GB GB8137510A patent/GB2089776B/en not_active Expired
- 1981-12-18 PH PH26650A patent/PH19383A/en unknown
- 1981-12-21 JP JP56205359A patent/JPS57131332A/en active Granted
- 1981-12-21 FR FR8123808A patent/FR2496700A1/en not_active Withdrawn
- 1981-12-21 AU AU78718/81A patent/AU548582B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6949232B2 (en) | 2002-05-31 | 2005-09-27 | Sherritt International Corporation | Producing cobalt (III) hexammine sulfate from nickel cobalt sulfides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS619374B2 (en) | 1986-03-22 |
| FR2496700A1 (en) | 1982-06-25 |
| PH19383A (en) | 1986-04-07 |
| AU548582B2 (en) | 1985-12-19 |
| US4401630A (en) | 1983-08-30 |
| JPS57131332A (en) | 1982-08-14 |
| GB2089776A (en) | 1982-06-30 |
| GB2089776B (en) | 1985-03-06 |
| AU7871881A (en) | 1982-07-01 |
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